High performance liquid rocket propellant

ABSTRACT

Disclosed is a high performance hydrocarbon fuel characterized by a hydrogen content greater than 14.3% by weight, a hydrogen to carbon atomic ratio greater than 2.0 and/or a heat of combustion greater than 18.7 KBtu/lb. The disclosed fuels generally have a paraffin content that is at least 90% by mass and a C 12 -C 20  isoparaffin content of at least 40% by mass.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.61/615,088, filed Mar. 23, 2012, which is incorporated herein byreference.

FIELD OF THE DISCLOSURE

The present disclosure relates generally to high performance liquidpropellants, and more particularly to high performance liquidpropellants suitable for use in rockets and hypersonic vehicles havingair breathing engines.

BACKGROUND

Liquid fuel as a propellant for rockets has been used to provide therequired thrust for many years. Liquid propellants have an advantageover solid propellants because the engine can be started and stopped bycontrolling the fuel flow to the combustor. In the liquid-fueled rocketengine, the fuel is burned in a fuel rich environment with an oxidant,usually liquid oxygen (LOX), to provide thrust generated by high speedejection of exhaust gases. In a rocket application, the fuel may besubjected to high environmental temperatures such as when the fuel isused as a coolant prior to combustion, and may decompose resulting inunwanted deposits, gums, foulants or the like. Therefore, the fuels usedas rocket propellants should exhibit good thermal stability.

An improvement in thermal stability as compared with more conventionalfuels (e.g., RP-1) is particularly important for fuels that are intendedfor use with reusable rocket engines and in air breathing hypersonicvehicles that employ the fuel as a coolant to help reduce the hightemperatures of airframe structures and engine components that aredeveloped during hypersonic flight. The term “air breathing” refers to avehicle having an engine that is configured to receive air from theatmosphere to be used in combustion of a fuel, and encompasses vehicleshaving various jet engines, such as ramjets, scramjets, etc.

The specific impulse (I_(sp)) is a performance measure for rocketpropellants that is equal to units of thrust produced during ejection ofexhaust gases from a rocket engine per unit weight of propellantconsumed per unit of time, and therefore specific impulse is measured inunits of time (e.g., seconds). I_(sp) can be used to determine thepayload that a rocket can carry into orbit. Propellants with a higherspecific impulse are desirable in order to deliver a payload into adesired orbit at a minimum cost. It is also desirable that the fuelburns or combusts cleanly and does not form deposits when a portion ofthe fuel is used for driving a turbine to operate a pump to deliver thefuel to the rocket engine.

Rocket scientists have determined that the specific impulse can becalculated from the equation:

$I_{sp} = {9.80\sqrt{\frac{T_{c}}{M}}\sqrt{\frac{k}{k - 1}}\sqrt{1 - \left( \frac{P_{e}}{P_{o}} \right)^{\frac{k - 1}{k}}}}$

Where,

M=a weighted average of the molecular weights of the combustion products

T_(c) is the combustion chamber temperature in degrees Rankine

k=C_(p)/C_(v) is the ratio of specific heats of the combustion products

P_(e)/P_(o)=ratio of external pressure to combustion chamber pressure

Therefore, to achieve highest I_(sp) it is desirable to have a highcombustion temperature (high net heat of combustion) and have combustionproducts with a lowest possible molecular weight. For example, maximumI_(sp) for any liquid propellant is provided by liquid hydrogen fuel,with oxygen as oxidant, because the product of combustion is only water(M=18). In contrast, a hydrocarbon fuel results in combustion productscomprising CO₂ (M=44), CO (M=28) and water. Therefore, to maximizeI_(sp), the hydrocarbon fuel must have a high hydrogen content (i.e. ahigh H/C atomic ratio) and it must burn such that CO₂ formation andunburned hydrocarbons are minimized. To minimize CO₂ generation andmaximize carbon monoxide generation, the rocket engine is designed tocombust the fuel under fuel rich conditions.

The disclosed formulations are capable of producing a higher I_(sp) thanthat provided by a conventional petroleum based refined kerosene calledRP-1. The RP-1 specifications were developed for military purposes asMIL-P25576 in 1957 and set a broad criterion for propellant propertieswith higher density, cleaner burning, ease of handling and performancerelative to kerosene jet fuel. Commercially available RP-1 fuels arelimited to a hydrogen content of about 14 wt. %, a hydrogen to carbonatomic ratio (H/C) less than 2.0, a heat of combustion less than 18.7KBtu/lb and can have up to 5 percent by volume aromatics and 2 percentby volume olefins. This conventional RP-1 fuel can also contain up to 30ppm (weight basis) sulfur. The aromatics and olefins can cause depositsand coke formation in the cooling chambers and sulfur can cause rapidcorrosion.

Previously, cycloalkanes, such as 1,2-diethylcyclohexane (DECH), whichhave optimum density and combustion properties, were added to refinedkerosene to produce a rocket propellant. However, DECH has a molecularformula of C₁₀H₂₀ with a density of about 0.80 g/cm³ while only havingan H/C atomic ratio of 2.0. Therefore, addition of DECH to conventionalRP-1 does not provide a great improvement. Further, DECH is not readilyavailable in large quantities. Substituted cycloalkanes are alsobelieved to produce combustion chamber products with a higher molecularweight than the breakdown products from isoparaffins.

SUMMARY OF THE DISCLOSURE

Disclosed are high performance liquid hydrocarbon fuels suitable for usein rocket engines, including those used for defense and spaceexploration. The disclosed high performance fuels are also applicable tothe aviation industry, such as for use with air breathing hypersonicvehicles. Also disclosed are methods for formulating high specificimpulse liquid fuels.

In accordance with certain embodiments, a hydrocarbon fuel having ahydrogen content greater than 14.3% on a weight (mass) basis areprovided, e.g., greater than 14.5% or 15% by mass.

In certain embodiments, the hydrocarbon fuel has a hydrogen to carbonatomic ratio greater than 2.0 (e.g., greater than 2.05 or greater than2.1).

In certain embodiments, the hydrocarbon fuel has a heat of combustiongreater than 18.7 KBtu/lb (e.g., greater than 18.8 KBtu/lb or greaterthan 18.9 KBtu/lb).

In certain embodiments, the hydrocarbon fuel has a total paraffincontent that is at least 90% by mass (e.g., at least 95% by mass or atleast 99% by mass), and an isoparaffin content that is at least 40% bymass (e.g., at least 50% by mass, at least 60% by mass, at least 70% bymass, or at least 75% by mass).

In certain embodiments, the hydrocarbon fuel is a blend of anisoparaffin and a highly paraffinic kerosene.

In certain exemplary embodiments, the isoparaffin blended with thekerosene is comprised of at least one isododecane, at least oneisohexadecane, at least one isoeicosane, or mixture of these.

In certain other embodiments, the hydrocarbon fuel is a blend of anisoparaffin and a naphthenic kerosene.

In certain embodiments, the fuel is used as a propellant in a vehiclehaving a rocket engine.

In certain embodiments, branched alkanes (isoparaffins) are blended withother base fuels to improve the performance characteristics of the basefuel (e.g., fuel density, heat of combustion, specific impulse anddeposit forming properties during catalytically induced endothermicpyrolytic decomposition for cooling applications).

Other features and advantages of the present disclosure will becomereadily appreciated as the same becomes better understood after readingthe following description.

DESCRIPTION

Formulations for high energy rocket fuels containing highly branchedparaffinic (i.e., isoparaffinic) chemical components, used individuallyor in combination with each other or in combination with highlyparaffinic refined kerosene or in combination with commerciallyavailable RP-1 fuel, are described herein. The hydrogen content and H/Catomic ratio of the new fuel is higher than conventional RP-1 fuelresulting in a greater heat of combustion. The sulfur, aromatics andolefin contents of these propellants are also lower, since thesecomponents are more susceptible to degradation in typical rocketpropulsion application environments. The net impact being that the novelformulations disclosed herein produce a significantly better propellantthan conventional RP-1 fuel for certain rocket and air breathinghypersonic vehicle applications. Advantageously, the fuel disclosedherein burns smoke free. The lower density of the isoparaffin materialmay require an increased volume of the fuel in the rocket, or theaddition of higher density fuel components.

The fuels disclosed herein comprise isoparaffins, such as isododecane,isohexadecane, isoeicosane, and/or highly refined and very paraffinickerosene streams with a high isoparaffin content. These components canbe used individually or in combination with each other. These componentsinherently have or can be selected to have a very low sulfur content,such that they can be combined with conventional fuels (e.g., RP-1 fuel)and/or other fuel components to provide a high performance liquid fuelthat has a sulfur content that is substantially lower than that ofconventional hydrocarbon liquid fuels.

The isoparaffins have a high hydrogen content and provide a higher H/Catomic ratio, higher heat of combustion, bum faster and cleaner, areeasier to handle and exhibit improved I_(sp) as compared withconventional RP-1 fuel. It is expected that the branched paraffiniccharacter of these fuels will provide exhaust gases with a lowermolecular weight than conventional RP-1 fuel. It is believed that themore highly branched paraffins provide a higher heat of combustion thantheir linear isomers or more lightly branched paraffin isomers. Lowermolecular weight isoparaffins provide a higher hydrogen content and H/Catomic ratio, and therefore provide exhaust products with lower averagemolecular weight and thus higher specific impulse, while highermolecular weight isoparaffins provide higher energy density. It isbelieved that the use of isoparaffins having from about 12 to about 24carbon atoms is desirable, and that compositions comprising at least 50%isoparaffins having from 12 to 20 carbon atoms by weight are useful forachieving a combination of improved specific impulse and energy density.Such fuels typically have a boiling point range of at least 100° F., andcan have a boiling point range greater than 130° F., 135° F. or 140° F.Desirably, the new fuels disclosed herein have a density (specificgravity) that is at least 0.76 or at least 0.77.

The fuels disclosed herein are characterized by having a highisoparaffin content, hydrogen content, H/C atomic ratio and heat ofcombustion. Conventional RP-1 fuels are limited to a hydrogen content ofabout 14 wt. %, an H/C atomic ratio less than 2.0, a net heat ofcombustion of less than 18.7 KBtu/lb. The fuel components that can besubstituted for conventional RP-1 fuel, can be used singly or incombination with one another; and have a hydrogen content, H/C atomicratio, and heat of combustion values that are superior to conventionalRP-1 fuels. The resulting novel fuels may have a hydrogen contentgreater than 14.3 percent by mass, and/or a net heat of combustiongreater than 18.7 KBtu/lb. For example, the hydrogen content can begreater than 14.5 percent by mass, or even greater than 15 percent bymass. As another example, the net heat of combustion can be greater than18.8 KBtu/lb, or even greater than 18.9 KBtu/lb. The H/C atomic ratiocan be greater than 2.0, greater than 2.05, and even greater than 2.10.

Because of the high isoparaffin content of the fuels disclosed herein,these fuels typically have a low cycloparaffin content as compared withconventional RP-1 fuel. For example a conventional RP-1 fuel has about62% cycloparaffins by mass, whereas, the new fuels described hereintypically comprise less than 25% cycloparaffins by mass, and even lessthan 20% or 15% cycloparaffins by mass.

In one example, an isododecane comprised of mostly 2,2,4,6,6-pentamethylheptane has a density (specific gravity) of about 0.75g/cm³. This component with a formula of C₁₂H₂₆ was found to have a netheat of combustion of 18,964 Btu/lb. and a hydrogen content of 15.1 wt.% which equates to H/C atomic ratio of 2.13.

In another example, an isohexadecane comprised of mostly2,2,4,4,6,8,8-heptamethylnonane (HMN) has a density (specific gravity)of about 0.79 g/cm³. This component with a formula of C₁₆H₃₄ was foundto have a net heat of combustion of 18964 Btu/lb. and had a hydrogencontent of 14.9 wt. % which equates to a H/C atomic ratio of 2.10.

In another example, an isoeicosane having a density of 0.8179 g/cm³ hasa formula of C₂₀H₄₂ and is expected to have a hydrogen content of 14.89wt. %, H/C atomic ratio of 2.10 and a high heat of combustion.

Refined kerosenes for formulating the fuels disclosed herein aretypically highly paraffinic and have a high isoparaffinic content withsome naphthenic content and little or no aromatics. For example, ahighly refined stream derived from a highly paraffinic crude had ahydrogen content of 14.7 percent by weight, H/C atomic ratio of 2.06 anda net heat of combustion of 18,852 Btu/lb. A “highly isoparaffinickerosene” refers to a kerosene comprising at least 50% isoparaffins byweight.

In another example, if the density of the fuel formulated using thecomponents identified above is less than optimum, a more naphthenickerosene can be added to increase the density of the blended fuel at aslight detriment to H/C atomic ratio value. One such naphthenic kerosenewas found to have 13.9% hydrogen, an H/C atomic ratio of 1.94 and a heatof combustion of 18,641 Btu/lb. This naphthenic kerosene had only 21.9percent by volume isoparaffins and normal-paraffins, and about 77percent by volume naphthenic components. A naphthenic kerosene is akerosene comprised primarily (at least 50 percent by mass) of naphtheniccompounds (i.e., cycloalkanes having general formula C_(m) H_(2(m+1−r)),where m is the number of carbon atoms and r is the number of rings inthe cycloalkane).

As another alternative, small amounts of 1,2-diethylcyclohexane (DECH)may be added to highly isoparaffinic compositions in amounts sufficientto provide blends having a higher mass density, and therefore a higherenergy density, without unacceptably reducing the heat of combustion.

Rocket fuels having a higher H/C atomic ratio than conventional RP-1fuels can also be formulated by the addition of isododecane,isohexadecane and isoeicosane to refined kerosenes.

In Table 1, the physical properties of two examples of rocket fuelsproduced using the formulations described herein (Blend H and Blend G1)are compared with an RP-1 fuel produced to MIL-P25576 requirements.

TABLE 1 New Rocket Propellant Compared with Typical RP-1 HF0824 RESULTSRESULTS RESULTS TEST METHOD UNITS Blend H Blend G1 Typical RP-1Distillation - IBP ASTM D86 ° F.      344.6      354.2      367.9  5% °F.      354.0      373.6      383.0 10% ° F.      356.0      377.6     386.3 20% ° F.      359.4      384.2      393.5 30% ° F.      363.7     393.4      399.4 40% ° F.      366.0      404.3      406.8 50% ° F.     369.8      417.6      415.3 60% ° F.      377.3      435.7     424.5 70% ° F.      391.5      451.6      435.0 80% ° F.      423.7     465.7      448.6 90% ° F.      462.7      470.7      467.5 95% ° F.     472.7      478.2      483.4 Distillation - EP ° F.      485.0     490.3      506.5 Recovery vol %       97.8       98.0       98.3Residue vol %       1.2       1.2       1.4 Loss vol %       1.0      0.8       0.3 Gravity ASTM D4052 °API       54.70       51.9      42.8 Specific Gravity ASTM D4052 —       0.7600       0.7713      0.8120 Flash Point ASTM D93 ° F.      133      149      144 Freezepoint ASTM D2386 ° F.   <−81     −44   <−94 Hydrogen ASTM D3343 wt %      15.06       15.07       14.29 Sulfur ASTM D5453 mg/kg     <1      2.4     <1 Mercaptan sulfur ASTM D3227 mg/kg     <3     <3     <3Composition, aromatics ASTM D1319 vol %     <5     <5     <5Composition, olefins ASTM D1319 vol %     <0.3       0.4       0.4Existent gum, washed ASTM D381 mg/100 mls     <1     <1     <1Particulate contaminant ASTM D5452 mg/l na na       0.37 Viscosity @-30°C. ASTM D445 cSt       6.866       9.138       9.645 Corrosion, CopperASTM D130 — 1a 1a 1a Water React Rating ASTM D1094 —       1 1b       1Net Heat of Combustion ASTM D240 BTU/lb     18934     18871     18659

TABLE 2 Compositional Analysis Data Typical Blend G1 HIRK RP-1Alkylbenzenes wt % wt % wt % Benzene <0.01 <0.01 <0.01 Toluene <0.01<0.01 <0.01 C2-Benzene <0.01 <0.01 <0.01 C3-Benzene 0.03 <0.01 <0.01C4-Benzene <0.01 <0.01 0.13 C5-Benzene <0.01 <0.01 0.02 C6+ Benzenes0.14 <0.01 <0.01 Total 0.17 <0.01 0.16 Alkylnaphthalenes Naphthalene<0.01 <0.01 <0.01 C1-Naphthalenes <0.01 0.02 <0.01 C2-C4 alkylnaphthalenes 0.02 0.04 <0.01 Total 0.03 0.06 <0.01 indans and tetralins0.07 0.12 0.25 iso-Paraffins C7 and lower-Iso- 0.03 <0.01 <0.01 C8-Iso-0.03 <0.01 <0.01 C9-Iso- <0.01 <0.01 0.02 C10-Iso- <0.01 <0.01 2.26C11-Iso- 0.57 0.16 6.44 C12-Iso- 37.05 3.15 7.89 C13-Iso- 9.57 14.688.15 C14-Iso- 21.08 32.48 5.18 C15-Iso- 8.27 12.80 3.03 C16-Iso- 1.221.89 0.71 C17 and greater 0.22 0.34 0.27 total isoparaffins 78.03 65.5033.95 Typical n-Paraffins G1 HIRK RP-1 n-C7 <0.01 <0.01 <0.01 n-C8 <0.01<0.01 <0.01 n-C9 <0.01 <0.01 0.06 n-C10 <0.01 <0.01 0.22 n-C11 0.23 0.351.54 n-C12 1.55 2.41 1.23 n-C13 3.76 5.82 0.25 n-C14 3.81 5.93 0.28n-C15 0.41 0.63 0.04 n-C16 0.05 0.08 <0.01 total n-paraffins 9.80 15.233.62 Cycloparaffins Monocycloparaffins 5.08 8.24 37.66 Dicycloparaffins5.91 8.51 19.72 bihexyls 0.28 0.49 2.47 Tricycloparaffins 1.07 1.76 2.35total cycloparaffins 12.33 19.00 62.20 100 100 100

The compositional analysis of the G1 Fuel listed in Table 1, asdetermined using a comprehensive gas chromatography technique (alsoreferred to as “GC×GC”), is provided in Table 2, along with thecompositional analysis of a highly isoparaffinic refined kerosene(“HIRK”) used to prepare the G1 Fuel, and the compositional analysis ofthe typical RP-1 fuel.

Formulation G1 may be produced by blending 40 percent by volumeisododecane with 60 percent by volume of the highly paraffinic kerosene(HIRK) described above.

Formulation H may be produced by blending 70 percent by volumeisododecane with 30 percent by volume of a highly paraffinic kerosenedescribed above.

Other suitable formulations generally include hydrocarbon fuelscomprising at least 40 percent by mass, at least 50 percent by mass, atleast 60 percent by mass, at least 70 percent by mass, or at least 75percent by mass isoparaffins. Examples include compositions comprising atotal paraffin content (iso-paraffins plus n-paraffins pluscycloparaffins) of at least 90 percent, 95 or 99 percent by mass whereinthe content of isoparaffins having from 12 to 20 carbon atoms is atleast 50 percent, at least 60 percent, at least 70 percent or at least75 percent by mass, and the cycloparaffin content is less than 35percent, less than 20 percent, less than 15 percent or less than 10percent by mass. Isoparaffins and normal-paraffins are hydrocarbons(molecules comprised of only hydrogen and carbon) having general formulaC_(n)H_(2n+2), where n is a positive integer. The term “isoparaffin”encompasses paraffins that are branched (i.e. paraffins in which atleast one carbon atom is bonded to at least three other carbon atoms).

Blends G1 and H are superior to the RP-1 shown in Table 1 except thatdensities of blends G1 and H are slightly lower. Blends with higherdensities can be formulated by adding isohexadecane and or isoeicosane,which have high densities, high H/C atomic ratio and high heats ofcombustion. For example, the densities of fuels G1 and H can beincreased by addition of isoeicosane without significantly sacrificingH/C atomic ratio or heat of combustion.

Substituted monocyclic or bicyclic paraffins such as1,2-diethylcyclohexane (DECH) or bicyclodecane (also known as decalin)may also be employed in amounts sufficient to increase mass and energydensities without significantly or undesirably reducing the heat ofcombustion of the fuels.

The disclosed novel liquid fuels are better than conventional RP-1 fuelsbecause they have a higher hydrogen content, a higher H/C atomic ratio,and a higher heat of combustion, with little or no aromatics, olefin orsulfur. Therefore, these fuels provide a higher I_(sp) with minimumcorrosion or coking and plugging of the cooling chambers and exhaustnozzle.

Additionally, the fuels described herein are believed to be well suitedfor applications in which the fuel is caused to flow throughmicrochannels having walls coated with a catalyst for inducingendothermic pyrolytic decomposition to cool engine components orairframe structures of rockets or air breathing hypersonic vehicles. Insuch applications, it may be desirable to employ a separation processfor removing trace amounts of oxygen-containing compounds such asketones, aldehydes or alcohols, such as by passing the fuel through asorption bed that comprises a material that selectively adsorbs orabsorbs oxygen-containing (polar) compounds. It is believed that amountsof oxygen-containing compounds in the fuel as low as about 200 to 300ppm (weight) can cause fouling during endothermic pyrolyticdecomposition of the fuel, causing overheating and potentiallycatastrophic failure of engine and/or airframe components. Theseparation process that may be employed can reduce the amount ofoxygen-containing compounds in the fuel composition to less than 200 ppm(weight), less than 100 ppm (weight), or even less then 50 ppm (weight).

The described embodiments are not limiting. Various modifications areconsidered within the purview and scope of the appended claims.

1. A hydrocarbon fuel having a range of components that provide aboiling point range of at least 100° F., and having a hydrogen contentgreater than 14.3% on a mass basis.
 2. A hydrocarbon fuel having a rangeof components that provide a boiling point range of at least 100° F.,and having a hydrogen to carbon ratio greater than 2.0 on an atomicbasis.
 3. The hydrocarbon fuel of claim 2 having a net heat ofcombustion greater than 18.7 KBtu/lb.
 4. A hydrocarbon fuel inaccordance with claim 3 which is a blend of an isoparaffin and a highlyparaffinic kerosene.
 5. The hydrocarbon fuel of claim 4, in which theisoparaffin is comprised of at least one isododecane, at least oneisohexadecane, at least one isoeicosane, or a mixture of these.
 6. Ahydrocarbon fuel in accordance with claim 3 which is a blend of anisoparaffin and a naphthenic kerosene.
 7. The hydrocarbon fuel of claim6, in which the isoparaffin is comprised of at least one isododecane, atleast one isohexadecane, at least one isoeicosane, or a mixture ofthese.
 8. (canceled)
 9. (canceled)
 10. A fuel composition comprising: atotal paraffin content of at least 90% by mass; and wherein thecomposition contains at least 40% by mass of isoparaffins having from 12to 20 carbon atoms.
 11. The composition of claim 10, in which a net heatof combustion is greater than 18,700 BTU/lb.
 12. The composition ofclaim 10, in which the hydrogen content is greater than 14.5% by mass.13. The composition of claim 10 wherein the total paraffin content is atleast 95% by mass.
 14. The composition of claim 10 wherein thecomposition contains at least 60% by mass of isoparaffins having from 12to 20 carbon atoms.
 15. The composition of claim 10 in which the totalparaffin content is at least 95% by mass, and wherein the compositioncontains at least 60% by mass of isoparaffins having from 12 to 20carbon atoms.
 16. The composition of claim 10 in which the totalparaffin content is at least 95% by mass, and wherein the compositioncontains at least 70% by mass of isoparaffins having from 12 to 20carbon atoms.
 17. The composition of claim 10 in which the totalparaffin content is at least 95% by mass, and wherein the compositioncontains at least 75% by mass of isoparaffins having from 12 to 20carbon atoms.
 18. The composition of claim 10 in which the totalparaffin content is at least 99% by mass, the net heat of combustion isat least 18,800 BTU/lb, and the specific gravity is at least 0.76. 19.The composition of claim 10 in which the total paraffinic content is atleast 99% by mass, the net heat of combustion is at least 18,900 BTU/lb,and the specific gravity is at least 0.77.
 20. The composition of claim10 which has been subjected to a separation process to reduce the amountof oxygen-containing compounds in the composition.
 21. The compositionof claim 20 in which the separation process comprises passing thecomposition through a sorption bed that comprises a material thatselectively adsorbs or absorbs oxygen-containing compounds.
 22. Thecomposition of claim 10 which comprises less than 200 ppm (weight) ofoxygen-containing compounds.